CN106457223A - High activity hydroprocessing catalyst - Google Patents
High activity hydroprocessing catalyst Download PDFInfo
- Publication number
- CN106457223A CN106457223A CN201580034100.9A CN201580034100A CN106457223A CN 106457223 A CN106457223 A CN 106457223A CN 201580034100 A CN201580034100 A CN 201580034100A CN 106457223 A CN106457223 A CN 106457223A
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- China
- Prior art keywords
- catalyst
- acid
- weight
- carbon monoxide
- olefin polymeric
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 133
- 230000000694 effects Effects 0.000 title abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 61
- 239000002184 metal Substances 0.000 claims abstract description 61
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 38
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 38
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 38
- -1 carboxyl carbon Chemical compound 0.000 claims abstract description 28
- 150000007524 organic acids Chemical class 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 238000007254 oxidation reaction Methods 0.000 claims description 21
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- 239000003921 oil Substances 0.000 description 21
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- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
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- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
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- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 2
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- 229910002703 Al K Inorganic materials 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- B01J37/20—Sulfiding
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/648—Fischer-Tropsch-type reactions
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- B01J2531/84—Metals of the iron group
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
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- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
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- C10G2300/1048—Middle distillates
- C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
The present disclosure relates to supported multimetallic catalysts for use in the hydroprocessing of hydrocarbon feeds and methods for preparing the catalysts. The catalyst is prepared with a catalyst precursor comprised of at least one group VIB metal, at least one group VIII metal, and an organic acid. The catalyst precursor is heat treated to partially decompose the organic acid and then sulfided. The catalyst has a high ratio of carboxyl carbon to total carbon (C)Carboxyl group/CTotal carbon) This is due to the unique post-metal calcination process employed during the manufacture of the catalyst. Thus, the hydroprocessing catalyst has lower weight percent loss on ignition, higher activity, and longer catalyst life.
Description
Technical field
It relates to being used for the support type multimetal reforming catalyst of hydrocarbon feed hydrotreating and being used for preparing this catalysis
The method of agent.This catalyst is with urging of being made up of at least one vib metals, at least one group VIII metal and organic acid
Prepared by agent precursor.This catalyst precarsor is heat-treated with decomposed organic acid, then cures.This catalyst has high
Carboxyl carbon and total carbon ratio (CCarboxyl/CTotal carbon), this is due to employing method for calcinating after the metal of uniqueness during manufacturing catalyst.
Background technology
Constantly increase with supervision and the operation pressure, lead to this area to need the hydrocarbon with low levels and low nitrogen level.
Oil refinery is using hydrotreating method come from hydrocarbon flow (such as Petroleum, kerosene, diesel oil, gas oil, vacuum gas oil (VGO)
(VGO) and reduced crude (reduced crude)) in remove hetero atom (such as sulfur and nitrogen).
Hydrotreating is typically accomplished by:In the case of there are hydrogen-containing treat gas, in High Temperature High Pressure
Hydrocarbon feed is made to contact with suitable hydrotreating catalyst in hydrotreating reaction container or region under hydroprocessing condition, with
Produce and there is the sulfur of desired level and/or the product of nitrogen.
Conventional hydro processes vib metals and the conduct promotion that catalyst usually contains in refractory support (as aluminium oxide)
One or more group VIII metal of agent.It is particularly well-suited to hydrodesulfurization (HDS) and the hydrotreating of hydrodenitrogeneration (HDN)
Catalyst usually contains the molybdenum being promoted on alumina or tungsten with metal (as cobalt, nickel, ferrum or combinations thereof).When restriction specification
When being hydrodesulfurization, the most frequently used catalyst promoting molybdenum on alumina with cobalt, and promote the catalysis of molybdenum on alumina with nickel
Agent is usually used in hydrodenitrogeneration, part aromatic hydrocarbons saturation and hydrodesulfurization.
This area has always a demand for for more active and more effectively removing hetero atom (as nitrogen and sulfur) from hydrocarbon flow
Catalyst.
Content of the invention
In one aspect, there is provided a kind of side of the carbon monoxide-olefin polymeric being applied to hydrotreating hydrocarbon feed for preparation
Method, the method includes:A () uses aqueous impregnation inorganic catalyst support, this aqueous solution contains the vib that (i) is selected from Mo and W
The salt of metal, (ii) are selected from the salt of group VIII metal and (iii) organic acid of Co and Ni;B () is dried this impregnated catalysis
Agent carrier, thus obtain the metal organic component in dried catalyst precursor;C () calcines this dry catalyst in oxygen-containing atmosphere
Precursor certain time simultaneously reaches uniform temperature so that be enough to some but not all organic portion aoxidizing in this metal organic component
Point, thus obtaining the catalyst precarsor of partial oxidation, the catalyst precarsor of this partial oxidation has (i) and is more than 1 to 20 weight %
Loss on ignition and (ii) at least 0.10 carboxyl carbon and total residual carbon ratio (CCarboxyl/CTotal carbon) (by X-ray photoelectron spectroscopy
Measure);And under conditions of vulcanization, (d) in the presence of vulcanizing agent, vulcanize the catalyst precarsor of this partial oxidation, thus obtain
The carbon monoxide-olefin polymeric of sulfuration.
On the other hand, there is provided a kind of carbon monoxide-olefin polymeric, it comprises:(a) inorganic catalyst support;And (b) portion
Divide the metal organic component of oxidation;Wherein said carbon monoxide-olefin polymeric have (i) be more than 1 to 20 weight % loss on ignition and
(ii) at least 0.10 carboxyl carbon and total residual carbon ratio (CCarboxyl/CTotal carbon) (being measured by X-ray photoelectron spectroscopy).
In another aspect, there is provided a kind of method for hydrotreating hydrocarbon feed, including:Under hydroprocessing conditions
Raw material is made to contact with hydrotreating catalyst, to produce the effluent of hydrogenated process, wherein this hydrotreating catalyst comprises:
(a) inorganic catalyst support;And the metal organic component of (b) partial oxidation;Wherein this catalyst has (i) more than 1 to 20
The carboxyl carbon of the loss on ignition of weight % and (ii) at least 0.10 and total residual carbon ratio (CCarboxyl/CTotal carbon) (by x-ray photoelectron
Spectroscopy measures).
Specific embodiment
Following term will use throughout the specification, and will have following meanings, except as otherwise noted.
Term " hydrotreating " refers to the catalysis process generally carrying out in the presence of free hydrogen, wherein when for locating
Reason hydrocarbon feed when, its main purpose be remove from raw material various metal pollutants (as arsenic), hetero atom (as sulfur, nitrogen and oxygen) with
And aromatic compounds.In general, in hydroprocessing operations, the cracking of hydrocarbon molecule (that is, is made bigger hydrocarbon molecule rupture
The hydrocarbon molecule of Cheng Geng little) be down to minimum.For purposes of this discussion, term " hydrotreating " refers to that conversion ratio therein is 20%
Or lower hydrogenation process operation, the scope of wherein " conversion ratio " is related to the raw material that boiling point is higher than reference temperature (for example, 371 DEG C)
Percentage ratio, described raw material be converted into boiling point be less than reference temperature product.
Term " organic acid " refers to containing at least one carboxylic acid functional (for non-ionised form (as-COOH), ionizing
Form (such as-COO-) or their salt) molecular entity.
Term " catalyst precarsor " refers to the catalyst of sulphided form.However, being not excluded for unvulcanised shape using this statement
The fact that catalyst of formula also has catalysis characteristicses.
Term " overall dry weight (bulk dry weight) " refers to that material is calcined 30 minutes under the high temperature more than 1000 DEG C
Weight afterwards.
As used herein, the numbering plan of each race of the periodic table of elements is in Chem.Eng.News, 63 (5), 27 (1985) (《Change
Learn and Engineering News Record》, volume 63, the 5th phase, page 27,1985) disclosed in.
In general, hydrotreating catalyst has vib metals component and group VIII metal component by deposition thereon
Carrier constitute.The most frequently used vib metals are molybdenum and tungsten, and cobalt and nickel are conventional group VIII metals.Accelerator is (such as
Phosphorus) it also is present in this catalyst.
Suitable support material for disclosure catalyst includes porous, inorganic refractory material, such as aluminium oxide, titanium dioxide
Silicon, carborundum, amorphous silica-alumina and crystalline silica-aluminium oxide, silica-magnesia, aluminum phosphate,
Boron oxide, titanium dioxide, zirconium oxide etc., and their mixture and cogelled.Preferably carrier includes silicon dioxide, oxidation
Aluminum, alumina silica and crystalline silica-aluminium oxide, especially classify as those materials of clay or zeolitic material.
For the purpose of this disclosure, preferred carrier material includes aluminium oxide, silicon dioxide and alumina silica, especially
Aluminium oxide or silicon dioxide.
Suitable vib metals for disclosure catalyst include chromium (Cr), molybdenum (Mo) and tungsten (W).Preferably, should
Vib metals are selected from Mo and W, it is highly preferred that this vib metals is Mo.This vib metals component can for oxide,
Oxyacid or the ammonium salt of oxo-anions or many oxygen anions.Overall dry weight based on catalyst in terms of metal-oxide, should
The amount of the vib metals component adopting in catalyst is usually 5 to 50 weight % (for example, 10 to 40 weight % or 15 to 30
Weight %).
For disclosure catalyst suitable group VIII metal include base metal ferrum (Fe), cobalt (Co) and nickel (Ni) with
And precious metal palladium (Pd) and platinum (Pt).Preferably, this group VIII metal is base metal, it is highly preferred that this group VIII gold
Belong to and be selected from Co and Ni.This group VIII metal component is usually oxide, hydroxide or salt, preferably salt.Based on catalyst
Overall dry weight in terms of metal-oxide, the amount of the group VIII metal component in disclosure catalyst is usually 1 to 20 weight
Amount % (for example, 2 to 10 weight %).
Based on the overall dry weight of catalyst, the total amount of the metal oxide materials in disclosure catalyst is 1 to 50 weight
Amount %.The amount of group VIII and vib metals can pass through atomic absorption spectrography (AAS) (AAS), energy dispersion X-ray analysis method
(EDX), inductively coupled plasma mass spectrometry (ICP-MS) and/or x-ray fluorescence method (XRF) measure.Illustrative metal combines
Including Co-Mo, Co-W, Co-Ni-Mo, Co-Ni-W, Ni-Mo, Ni-W and Ni-Mo-W.
The hydrotreating catalyst of the disclosure can contain phosphorus component as accelerator.There is phosphorus in catalyst and can improve hydrogenation
Denitrification activity.When there is phosphorus compound, overall dry weight based on catalyst with P2O5Meter, the phosphatization adopting in catalyst is closed
The amount of thing is usually 1 to 10 weight % (for example, 5 to 10 weight %).Phosphorus can be mixed by procedure below in any suitable manner
Enter in catalyst:Catalyst is made to contact with appropriate phosphorous acidic components during the either phase of its formation stages, described
Before phosphorous acidic components are such as Metaphosphoric acid, pyrophosphoric acid, phosphorous acid, orthophosphoric acid, triphosphoric acid, four phosphoric acid or various phosphorous acid
Body (such as ammonium hydrogen phosphate (ammonium dihydrogen phosphate, diammonium phosphate, triammonium phosphate)).
In general, the method preparing conventional hydro process catalyst is characterised by for example in the following manner by carrier
Material is combined with metal component:First dipping and then calcined composite, metal component is converted into its oxide.For being hydrogenated with
Before process, generally by presulfiding of catalyst so that metal is converted into its sulfide.The hydrotreating catalyst of the disclosure passes through
Prepared by the following manner:Deposit in carrier material or on carrier material or form metal organic component, then this network of decomposed
Compound is to produce catalyst precursor composition.Vulcanized by using vulcanization technology and catalyst precarsor is converted into gained
Catalyst.
Metal organic component for forming catalyst comprises at least one organic acid and at least one has catalysis activity
Metal.Organic acid can form any organic of organic complex for the metal that can have catalysis activity with one or more
Acid.Such organic compound is it is well known that including organic monodentate, two teeth and multiple tooth joining in transition metal chemistry field
Body.Organic acid is believed to be helpful in and metal is effectively dispersed in whole carrier.Hydroxy carboxylic acid is the exemplary organic acid of a class.Hydroxyl
Yl carboxylic acid contains one or more carboxyls and one or more hydroxyl.The non-limitative example of suitable hydroxy carboxylic acid includes ethanol
Acid, lactic acid, glyceric acid, gluconic acid, malic acid, tartaric acid, glactaric acid and citric acid.Most preferably hydroxy carboxylic acid is lactic acid, Fructus Mali pumilae
Acid, tartaric acid and citric acid.
Can by any suitable routine techniquess by organic acid and vib and group VIII Metal loading on carrier,
For example impregnated by initial impregnated with method, pass through to adsorb from excessive steeping medium, pass through ion exchange etc., or combinations thereof.
Typical dipping approach is by initial impregnated with method.Particular order can be pressed successively by organic acid and vib and simultaneously or not
Group VIII metal is loaded on carrier.The amount of the organic acid being loaded on carrier material is usually vib and group VIII gold
0.05 to 5 mole times (for example, 0.1 to 4,0.25 to 3,0.5 to 2 or 0.5 to 1.5 mole times) of the total mole number belonging to.
Then the impregnated carrier of conventional drying technique (for example at a temperature of about 100 DEG C) drying can for example be passed through, directly
To removing substantially all of moisture (for example, be dried 2 to 6 hours).
In or on the carrier deposit and/or formed metal organic component after, by calcining partial oxidation or point
Solve the organic moiety of this metal organic component, before the catalyst of the partial oxidation that at least some residual carbon content is had with formation
Body.So-called " partial oxidation ", refers to a kind of impregnated carrier that is applied to cause the organic moiety part of metallo-organic complex
But the Technology for Heating Processing of incomplete thermal decomposition.Calcine technology is generally carried out at a temperature of less than carrier fusing point, and oxygen-containing
Carry out under atmosphere.In one embodiment, partial calcination 350 DEG C to 500 DEG C (for example, 350 DEG C to 450 DEG C, 360 DEG C extremely
500 DEG C or 360 DEG C to 500 DEG C) at a temperature of carry out 1 minute to 1 hour (for example, 5 minutes to 1 hour, 5 to 30 minutes or 5 to
15 minutes).The impregnated carrier being dried can be calcined in such as heating furnace (as rotary kiln, batch-type furnace), belt dryer etc..
Determine that a standard having obtained suitable hydrotreating catalyst is the catalyst precarsor of measurement partial oxidation
Percentage by weight loss on ignition (LOI).LOI is measuring of total volatile matter (substantially water and organic acid) present in sample.LOI
Test is carried out as follows:Sample is made to be exposed to 1 hour in oxygen-containing atmosphere under 1020 °F (549 DEG C), thus oxidation or decomposition are organic
All residual moistures in material or removing catalyst.Under 1020 °F (549 DEG C), the carrier of dipping is fired to more than 1 to 20
Weight % (for example, more than 1 to 10 weight %, more than 1 to 9 weight %, more than 1 to 8 weight %, more than 1 to 7 weight %, be more than
1 to 6 weight %, more than 1 to 5 weight %, 2 to 20 weight %, 2 to 10 weight %, 2 to 9 weight %, 2 to 8 weight %, 2 to 7
Weight %, 2 to 6 weight %, 2 to 5 weight %, 3 to 20 weight %, 3 to 10 weight %, 3 to 9 weight %, 3 to 8 weight %, 3
To 7 weight %, 3 to 6 weight % or 3 to 5 weight %, 4 to 20 weight %, 4 to 10 weight %, 5 to 20 weight % or 5 to 10 weights
Amount %) selected loss on ignition (LOI).
Determine that another standard having obtained suitable hydrotreating catalyst is the catalyst precarsor of measurement partial oxidation
Carboxyl carbon and total residual carbon ratio (CCarboxyl/CTotal carbon).C when the catalyst precarsor of partial oxidationCarboxyl/CTotal carbonRatio is at least 0.10
(for example, 0.10 to 0.50,0.10 to 0.45,0.10 to 0.40,0.10 to 0.35,0.10 to 0.30,0.10 to 0.25, at least
0.15th, 0.15 to 0.50,0.15 to 0.45,0.15 to 0.40,0.15 to 0.35 or 0.15 to 0.25), when, observe HDS/HDN
Increased activity.So-called herein " CCarboxyl/CTotal carbon", refer to the ratio measuring by X-ray photoelectron spectroscopy (XPS).
XPS data presented herein is collected by standard technique.Powder is fixed to the two-sided tape in sample panel
On, to be introduced in analysis vacuum chamber.The monochromatic Al K α x-ray source being scanned using PHI Quantera XPS on microprobe is received
Collection XPS spectrum.During being characterized, controlled using standard charge neutralisation (using low kinetic energy electronics and positive Ar ion)
Electric charge processed.Data is collected with sufficiently high spectral resolution (at least resolution of 1.0eV), to allow C 1s Photoelectron peak is gone
Convolution.Simplify program using normal data.After hydrocarbon peak position is corrected to by 284.6eV according to standard x PS data processor,
CCarboxylThe average peak position of component is 289.4eV.CTotal carbonSummation for each carbonaceous component (such as hydrocarbon, alcohol/ether and carboxylic acid).
Catalyst precarsor is converted into by gained catalyst by vulcanisation step (process), thus metal component is converted into it
Sulfide.In the context of the disclosure, phrase " vulcanisation step " is intended to including wherein by sulfur-containing compound addition catalyst group
In compound and wherein at least a portion metal component present in catalyst is by directly or after carrying out activation processing with hydrogen
It is converted into any processing step of sulphided form.Suitable sulfuration process is well known in the art.Vulcanisation step can be
Ex situ will be processed in the reactor of hydrocarbon charging using catalyst hydrogenation or occurs in situ, or with situ and ex situ combination
Mode occurs.
Ex situ sulfuration process occurs by wherein using the outside of the reactor of catalyst hydrogenation process hydrocarbon charging.?
In such technique, catalyst is made to contact with sulfur-containing compound (as polysulfide or elementary sulfur) outside reactor, if necessary
If, it is dried.In the second step, optionally in the case of there is charging, use in the reactor and at high temperature
Hydrogen treat material, with activated catalyst, i.e. make catalyst become sulfided state.
In-situ sulphiding technique is occurred in the reactor that will be processed hydrocarbon charging using catalyst hydrogenation wherein.Here, making
Catalyst in the reactor and at high temperature be mixed with vulcanizing agent (such as hydrogen sulfide or be decomposed into sulfuration under prevailing condition
The compound of hydrogen) hydrogen stream contact.Also can use and contain the sulfur-containing compound being decomposed into hydrogen sulfide under prevailing condition
Hydrocarbon charging mixing hydrogen stream.In the case of the latter, (can be mixed with containing the hydrocarbon charging adding vulcanizing agent by making catalyst
Material (spiked) hydrocarbon charging) contact carrys out sulphurized catalyst, and it is also possible to use without any sulfur-bearing hydrocarbon charging adding vulcanizing agent,
Because sulphur component will be converted into hydrogen sulfide in the presence of a catalyst present in charging.Various sulfuration skills may also be employed
The combination of art.Preferably use spike hydrocarbon charging.
Catalyst disclosed herein uses (for example, with spheroid or extrudate form) in a usual manner.Suitable type squeeze
The example going out thing (see, for example, United States Patent (USP) No.4,028,227) disclosed in pertinent literature.Be highly suitable for this paper is
Cylindrical particle (can be hollow or non-hollow) and symmetrically and asymmetrically many lobes granule (2,3 or 4 lobe).
Catalyst disclosed herein can be used for the hydrotreating of various difference hydrocarbon feeds, and to realize hydrodesulfurization, hydrogenation takes off
One or more of nitrogen, HDM and hydrogenation aromatics-removing.In hydroprocessing technique, under effective hydroprocessing condition
In the reaction zone of operation, hydrocarbon charging stream is made to contact with catalyst.
Catalyst disclosed herein can be used in any fixed bed, fluid bed and moving bed reaction system.However, from
From the point of view of device or operating aspect, it is preferred to use fixed bed.Additionally, can be by carrying out multiple hydrotreating (that is, by two or more
Individual reactor links together) realizing high desulfurization and denitrogenation level.
The example of suitable hydrocarbon feed includes being derived from or from petroleum crude oil, Tar sands, coal liquefaction, shale oil and hydrocarbon
Those of synthesis, such as reduced crude, hydrocrackates, raffinate, hydrotreating oil, normal pressure and vacuum gas oil (VGO), coking watt
This oil, reduced crude and decompression residuum, deasphalted oil, dewaxed oil, waxy stone, fischer-tropsch wax and their mixture.Suitably former
Expect in the range of relatively light fraction to heavy charge, such as gas oil, lubricating oil and residual oil.The non-limit of light fraction raw material
Property example processed includes Petroleum (typical boiling range is 25 DEG C to 210 DEG C), (typical boiling range is 150 DEG C to 400 to diesel oil
DEG C), kerosene or jet fuel (typical boiling range is 150 DEG C to 250 DEG C) etc..The non-limitative example of heavy charge includes subtracting
Pressure (or weight) gas oil (typical boiling range is 315 DEG C to 610 DEG C), raffinate, lubricating oil, recycle oil, waxy oil etc..Preferably
Hydrocarbon feed boiling range be 150 DEG C to 650 DEG C, such as 150 DEG C to 450 DEG C.
It is suitable to the hydrocarbon feed with the present invention is processed and include nitrogen pollutant and amounts of sulphur contaminants and other materials.Based on hydrocarbon feed
Weight, the nitrogen content of such charging can be in the range of 50 to 4000ppm nitrogen (for example, 500 to 2000ppm nitrogen).Nitrogen can be made
It is alkalescence and the appearance of non basic nitrogen material.The non-limitative example of alkaline nitrogen material may include quinoline and substd quinolines, non-alkaline
The non-limitative example of nitrogen material may include carbazole and substituted carbazole.Based on the weight of hydrocarbon charging stream, the sulfur content of hydrocarbon feed can
In the range of 50 to 40000ppm sulfur (for example, 5000 to 30000ppm sulfur).Sulfur generally will close as the sulfuration organically combining
Thing exists, aliphatic mercaptan, cycloalkanes mercaptan and aromatic mercaptans, sulfide, disulphide and polysulfide etc..Other organic knots
The sulphur compound closing includes heterocyclic sulfur compounds class, such as thiophene, Tetramethylene sulfide, benzothiophene and their higher homologue
And analog.The hydrocarbon feed being applied to this paper also can contain aromatic compounds, and based on the weight of hydrocarbon feed, this aromatic compounds is led to
Often existed with the amount of 10 to 60 weight %.
Being suitable to is the wax feed of boiling in lube range with the illustrative hydrocarbon raw material that the disclosure is processed, described lubrication
Oil be generally in the range of more than 650 °F (343 DEG C) 10% evaporate a little and more than 800 °F (426 DEG C) terminal (by ASTM D86 or
ASTM D2887 measures).These hydrocarbon feeds can be from mineral origin, synthesis source or both mixture.Suitable lubrication
The non-limitative example of oily raw material includes those from following source:Such as derive from the oil of solvent refining processes, such as residual
Fluid;The oil of partial solvent dewaxing;Deasphalted oil;Distilled oil;Vacuum gas oil (VGO);Coker gas oil;Waxy stone;Foot oil;And take-
Support wax.These raw materials also can have nitrogen pollutant and the amounts of sulphur contaminants of high-load.Can process in the method for the invention be based on into
The weight of material contains the nitrogen of at most about 0.25 weight % and the raw material of the sulfur of weight at most about 3.0 weight % based on charging.Wax
The high charging of content generally has the high viscosity index (HVI) being up to about 200 or more.Sulfur and nitrogen content can pass through ASTM respectively
D5453 and ASTM D4629 measures.
Representational hydroprocessing condition includes the temperature of 302 °F to 752 °F (150 DEG C to 400 DEG C), and such as 392 °F extremely
752 °F (200 DEG C to 400 DEG C);The pressure of 100 to 3000psig (0.69 to 20.68MPa), such as 200 to 2000psig
(1.38 to 13.79MPa);0.1 to 10h-1Liquid hourly space velocity (LHSV) (LHSV), such as 0.5 to 5h-1;And 500 to 10000SCF/B
(89 to 1780m3/m3) hydrogen processing gas speed, such as 1000 to 5000SCF/B (178 to 890m3/m3).
Hydrocarbon feed contacts with catalyst disclosed herein that to produce the hydrocarbon comprising at least gaseous products and hydrogenated process former
The effluent of the hydrogenated process of material.Strip the effluent of hydrogenated process, remove from the effluent of this hydrogenated process to
Few a part of gaseous product.Means for stripping the effluent of hydrogenated process are optional oneself to know spendable any stripping side
Method, technique or device.The non-limitative example of suitable gas stripping process, device and technique includes flash tank, dephlegmator, separation
Tank, steam extracting etc..
Example
Following illustrative example is nonrestrictive.
Example 1
The preparation of dipping solution
Add 116.7g citric acid in 400mL water in the round-bottomed flask equipped with agitator.By 194.75g nickelous carbonate
(49%Ni) add in above-mentioned solution.Then it is slowly added to 189.34g phosphoric acid (85%) in this solution, this solution is heated to
150°F.Then to addition 475.95g molybdenum trioxide in this solution.This solution is heated to about 190 °F to 210 °F, and in this temperature
Keep in the range of degree at least 1.5 hours, until this solution becomes clarification.Once this solution becomes clarification, it is cooled to less than 120 °F
And add other 272.8g citric acid, stir this mixture and clarify until this solution becomes.This solution is diluted to by deionized water
1000mL.Final MoO in this solution3Concentration is 0.4750g/mL.Analysis resulting solution shows its composition, and (metal is with oxygen as follows
Compound represents):Based on concentration in terms of weight % for the dry weight:NiO is 6.0;P2O5For 6.5;MoO3For 25.0.This solution contain with
Lower component ratio:Citric acid/(NiO+MoO3) (mol/mol) be 0.4.
Example 2
The preparation of the catalyst precarsor of partial oxidation
Two kinds of hydrotreating catalysts of preparation, a kind of (catalyst 1) is calcined after unique metal as herein described loading
Technique manufactures, and another kind of (catalyst 2) utilizes Conventional calcination technology to manufacture.
Prepare catalyst 1 and catalyst 2 as follows:Metal impregnation solution impregnation silicon dioxide-oxygen using preparation in example 1
Change the aluminum (SiO of 3 weight %2) carrier.Carrier is impregnated by initial impregnated with method.This silica-alumina carriers has following
Feature:Surface area 260m2/ g and N2Pore volume 0.81mL/g.
With identical Metal loading but prepare catalyst 1 and catalyst 2 under different calcining heats, thus obtaining different
LOI.
For catalyst 1, precursor is heated 10 minutes in atmosphere under 320 °F (160 DEG C), was warming up in 40 minutes
680 °F (360 DEG C), and keep 10 minutes under 680 °F, so that LOI is 5%.
For catalyst 2, precursor is heated 10 minutes in atmosphere under 320 °F (160 DEG C), was warming up in 40 minutes
1000 °F (538 DEG C), and keep 10 minutes under 1000 °F, so that LOI is 0-1%.
XPS measurement result shows, Ni is not observed in catalyst 1 or catalyst 23The sign that C exists.
The physical property of catalyst precarsor 1 and catalyst precarsor 2 is summarized in table 1.Described physical property is at 1000 °F
Measurement after calcining.It is as shown in the table, and between two kinds of catalyst, unique significant difference is the chemical speciation of carbon, wherein urges
Agent precursor 1 has higher carboxyl carbon relative concentration.
Table 1
Catalyst precarsor 1 and the physical property of catalyst precarsor 2
Catalyst precarsor 1 | Catalyst precarsor 2 (conventional) | |
Surface area, m2/g | 148 | 148 |
N2Pore volume, mL/g | 0.4 | 0.38 |
LOI when 1020 °F | 5 | 1 |
MoO3, weight % | 25.51 | 26.93 |
NiO. weight % | 6.37 | 6.64 |
P2O5, weight % | 7.14 | 6.9 |
Carboxyl carbon (CCarboxyl), mol | 1.37 | 0.33 |
Total carbon (CTotal carbon), mol | 7.11 | 4.08 |
CCarboxyl/CTotal carbon | 0.19 | 0.08 |
Example 3
The sulfuration of the catalyst precarsor of partial oxidation
By catalyst precarsor 1 and each autovulcanization of catalyst precarsor 2, to provide catalyst 1 and the sulfuration of catalyst 2 to urge respectively
Agent compositionss.Sulfuration program used is summarized as follows.
Liquid phase vulcanizes:Catalyst precarsor is dried 1 hour in nitrogen under 150 °F and atmospheric pressure.Catalyst is used 2.5
Weight %54 vulcanizing agents (Lubrizol Corp. (Lubrizol))/straight run (SR) diesel oil in hydrogen in
Moistening 1 hour under 250 °F and 500psig.It is carried out as follows cryogenic vulcanization:Make catalyst and 2.5 weight %
54/SR diesel oil is in 480 °F, 500psig and 1h-1LHSV under contact 30 hours.It is carried out as follows high temperature vulcanized:Make catalyst with
2.5 weight %54/SR diesel oil is in 650 °F, 2300psig and 2h-1LHSV under contact 8 hours.With 2.5
Weight %Temperature of reactor is down to 450 °F by 54/SR diesel oil, and keeps 2 hours at such a temperature.?
680 °F, 2300psig and 2.0h-1Lower output SR diesel oil, keeps 3 days.Gained is evaporated material send in unit, and temperature is risen to list
First running temperature.
Gas-phase presulfiding:Catalyst precarsor is dried 1 hour in nitrogen under 150 °F and atmospheric pressure, then in nitrogen
It is dried 0.5 hour under 450 °F and atmospheric pressure.It is carried out as follows cryogenic vulcanization:Make catalyst and the dimethyl disulfide of 6 weight %
(DMDS)/heptane is in hydrogen in 450 °F, 500psig and 4.0h-1Lower contact 4 hours.It is carried out as follows high temperature vulcanized:Make catalysis
The DMDS/ heptane of agent and 6 weight % is in hydrogen in 600 °F, 800psig and 4.0h-1Lower contact 4 hours.With 6 weight %
Temperature of reactor is down to 450 °F by DMDS/ heptane, and keeps 2 hours at such a temperature.In 680 °F, 2300psig and 2.0h-1
Lower output SR diesel oil, keeps 3 days.Gained is evaporated material send in unit, and temperature is risen to unit running temperature.
Example 4
HDS/HDN activity using catalyst 1 and the VGO of catalyst 2
Under process conditions listed by table 3 below, property listed by table 2 is had using catalyst 1 and catalyst 2 hydrotreating
VGO.
Table 2
The property of VGO charging
API | 17.2 |
S, weight % | 2.54 |
N, ppm | 2484 |
H weight % being recorded by NMR | 11.49 |
The tenor being recorded by ICP | |
Fe, ppm | 13.0 |
Na, ppm | 2.3 |
Ni, ppm | 1.2 |
V, ppm | 5.7 |
Simulation distillation (SimDist) (weight %), °F | |
0.5 | 472 |
5 | 628 |
50 | 820 |
95 | 988 |
EP | 1021 |
Table 3
Hydroprocessing technique condition
The catalyst being vulcanized using vulcanizing gentle mutually sulfuration by liquid phase, obtains hydroprocessing test results and (represents
For opposite bank accumulated amount (RVA)), it is summarized in respectively in table 4 below and table 5.
Table 4
The HDS/HDN activity of the catalyst being vulcanized by liquid phase sulfuration
Catalyst 1 | Catalyst 2 (conventional) | |
RVA HDN | 116 | 97 |
RVA HDS | 117 | 100 |
Table 5
The HDS/HDN activity of the catalyst being vulcanized by gas-phase presulfiding
Catalyst 1 | Catalyst 2 (conventional) | |
RVA HDN | 112 | 97 |
RVA HDS | 112 | 100 |
As shown in table 4 and table 5, the HDN/HDS activity of catalyst 1 is significantly better than conventional catalyst 2.
For the purpose of this specification and the appended claims, except as otherwise noted, otherwise represent quantity, percentage ratio or
Used in all numerals of ratio and specification and claims, other numerical value are interpreted as in all cases by art
Language " about " is modified.Therefore, unless indicated to the contrary, the numerical value otherwise illustrating in description below and appended claims
Parameter is approximation, and it can change according to the desirable characteristics that hope obtains.It should be noted that as in this specification and appended right
Used in claim, singulative " ", " one " and " being somebody's turn to do " include plural thing, unless be limited to clearly and unambiguously
One referring to thing.As used herein, term " inclusion " and its grammatical variants are nonrestrictive so that the project in list is enumerated
It is not excluded for being substituted or added to other similar items of Listed Items.As used herein, term " inclusion " be intended to including
The element marking after this term or step, but this dvielement any or step are nonexhaustive, and embodiment may include
Other elements or step.
Except as otherwise noted, otherwise may select from single component or element, material or the other components of component mixture
Belong to enumerates all possible subgenus combination being intended to including listed component and their mixture.
Can patentable scope be defined by the claims, and may include those skilled in the art can think and other
Example.If other examples such have the literal description identical structural detail with claims, or if they wrap
Include the equivalent structural elements with the literal description no essence difference of claims, then these other examples are in claims
In the range of.In degree reconcilable with this paper, all quotations being mentioned above are hereby incorporated by herein.
Claims (15)
1. a kind of carbon monoxide-olefin polymeric, comprises:
(a) inorganic catalyst support;And
The metal organic component of (b) partial oxidation;
Wherein said carbon monoxide-olefin polymeric is had (i) and is such as penetrated by X more than the loss on ignition of 1 weight % to 20 weight % and (ii)
At least 0.10 carboxyl carbon that Photoelectron Spectroscopy measures and total residual carbon ratio (CCarboxyl/CTotal carbon).
2. carbon monoxide-olefin polymeric according to claim 1, described compositionss also comprise phosphorus component.
3. carbon monoxide-olefin polymeric according to claim 2, the wherein overall dry weight based on described catalyst with P2O5Meter,
Described phosphorus component is existed with the amount of 1 weight % to 10 weight %.
4. carbon monoxide-olefin polymeric according to claim 1, the metal portion of the metal organic component of wherein said partial oxidation
Subpackage contains at least one vib metals and at least one group VIII metal.
5. carbon monoxide-olefin polymeric according to claim 4, wherein said at least one vib metals are Mo, and described
At least one group VIII metal is Ni.
6. carbon monoxide-olefin polymeric according to claim 1, wherein before partial oxidation, the having of described metal organic component
Machine part is hydroxy carboxylic acid.
7. carbon monoxide-olefin polymeric according to claim 6, wherein said hydroxy carboxylic acid be selected from glycolic, lactic acid, glyceric acid,
Gluconic acid, malic acid, tartaric acid, glactaric acid and citric acid.
8. carbon monoxide-olefin polymeric according to claim 1, described compositionss have the burning more than 1 weight % to 10 weight %
Vector.
9. carbon monoxide-olefin polymeric according to claim 1, described compositionss have 0.1 to 0.5 CCarboxyl/CTotal carbonRatio.
10. a kind of method for preparing carbon monoxide-olefin polymeric according to claim 1, including:
A () uses aqueous impregnation inorganic catalyst support, described aqueous solution contains (i) selected from the vib metals of Mo and W
Salt, (ii) are selected from the salt of group VIII metal and (iii) organic acid of Co and Ni;
B () is dried described impregnated catalyst carrier, thus obtaining the metal organic component in dried catalyst precursor;
C () is calcined described dried catalyst precursor certain time in oxygen-containing atmosphere and is reached uniform temperature so that be enough to aoxidize
Some but not all described organic moiety in described metal organic component, thus obtaining the catalyst precarsor of partial oxidation, institute
The catalyst precarsor stating partial oxidation has (i) and is more than the loss on ignition of 1 weight % to 20 weight % and (ii) as by X-ray
At least 0.10 carboxyl carbon that electron spectroscopy for chemical analysis measures and total residual carbon ratio (CCarboxyl/CTotal carbon);And
D (), in the presence of vulcanizing agent, vulcanizes the catalyst precarsor of described partial oxidation under conditions of vulcanization, thus obtaining sulfuration
Carbon monoxide-olefin polymeric.
11. methods according to claim 10, wherein said organic acid is hydroxy carboxylic acid.
12. methods according to claim 11, wherein said hydroxy carboxylic acid is selected from glycolic, lactic acid, glyceric acid, glucose
Acid, malic acid, tartaric acid, glactaric acid and citric acid.
13. methods according to claim 10, wherein said calcining is carried out at a temperature of 350 DEG C to 500 DEG C.
14. methods according to claim 10, wherein said calcining is carried out 5 to 15 minutes.
A kind of 15. methods for hydrotreating hydrocarbon feed, including:Make described raw material and hydrotreating under hydroprocessing conditions
Catalyst contacts, and to produce the effluent of hydrogenated process, wherein said hydrotreating catalyst comprises according to claim 1 institute
The carbon monoxide-olefin polymeric stated.
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JP2005000873A (en) * | 2003-06-13 | 2005-01-06 | Catalysts & Chem Ind Co Ltd | Method for producing hydrotreating catalyst composition of hydrocarbon |
CN101330972A (en) * | 2005-12-14 | 2008-12-24 | 先进炼制技术有限公司 | Method of making hydroprocessing catalyst |
CN101563437A (en) * | 2006-12-19 | 2009-10-21 | 埃克森美孚研究工程公司 | High activity supported distillate hydroprocessing catalysts |
CN103769220A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of catalyst for distillate oil hydro-treatment |
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KR20160147897A (en) | 2016-12-23 |
JP6574201B2 (en) | 2019-09-11 |
JP2020011235A (en) | 2020-01-23 |
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CA2946733C (en) | 2019-06-11 |
SG11201608544QA (en) | 2016-11-29 |
JP6874073B2 (en) | 2021-05-19 |
JP2017518172A (en) | 2017-07-06 |
EP3134205A1 (en) | 2017-03-01 |
CA2946733A1 (en) | 2015-10-29 |
WO2015164464A1 (en) | 2015-10-29 |
CN117138845A (en) | 2023-12-01 |
EP3134205B1 (en) | 2020-11-04 |
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